Although　both　step-scheme　(S-scheme)　heterojunction　and　metal–organic　framework　(MOF)　photocatalysts　have　been　intensively　studied,　few　efforts　have　been　devoted　to　combining　them　to　establish　high-performance　MOF-based　S-scheme　photocatalysts.　In　this　work,　binary　Ag@MIL-68(Fe)　(Ag@MFe)　hybrids　were　first　fabricated　by　decorating　Ag　nanoparticles　(Ag　NPs)　onto　MIL-68(Fe),　an　Fe-based　MOF.　Owing　to　the　high　specific　surface　area　of　MIL-68(Fe),　the　plasmonic　Ag　NPs　were　uniformly　distributed　on　its　surface.　Then,　AgBr　particles　were　deposited　on　the　Ag@MFe　hybrids　via　precipitation　to　form　the　final　ternary　sandwich-like　hierarchical　AgBr-Ag@MFe　photocatalyst.　The　30　%AgBr-1.5　%Ag@MFe　sample　exhibited　excellent　photocatalytic　performance　for　the　degradation　of　rhodamine　B　under　visible　light　irradiation　(λ　≥　420　nm),　with　an　effectiveness　9.2　and　2.1　times　higher　than　those　of　the　original　MIL-68(Fe)　and　binary　1.5　%Ag@MFe　hybrid,　respectively.　Furthermore,　30　%AgBr-1.5　%Ag@MFe　performed　as　a　high-efficiency　bifunctional　photocatalyst　towards　the　detoxification　of　water　contaminants　(mixture　of　a　dye　and　Cr(VI)).　The　significantly　enhanced　photoactivity　was　attributed　to　the　effective　spatial　separation　of　photogenerated　electron–hole　pairs　via　S-scheme　charge　transfer.　Moreover,　the　plasmonic　Ag　NPs　assembled　into　the　contact　interface　of　AgBr　and　MIL-68(Fe)　enhanced　the　vectorial　interfacial　electron　transfer.　The　formation　of　an　S-scheme　heterojunction　was　supported　by　X-ray　photoelectron　spectroscopy　and　electron　spin　resonance　studies.　This　novel　bifunctional　AgBr-Ag@MIL-68(Fe)　hybrid　photocatalyst　system　not　only　provides　new　opportunities　for　environmental　remediation　but　also　highlights　a　promising　strategy　to　construct　high-efficiency　S-scheme　photocatalysts.　©　2021　Elsevier　B.V.